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Aromatization of Hydrocarbons by Oxidative Dehydrogenation Catalyzed by the Mixed Addenda Heteropoly Acid H5pmo10v2040

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Aromatization of Hydrocarbons by Oxidative Dehydrogenation Catalyzed by the Mixed Addenda Heteropoly Acid H5pmo10v2040 J. Org. Chem. 1989,54, 4607-4610 4607 Aromatization of Hydrocarbons by Oxidative Dehydrogenation Catalyzed by the Mixed Addenda Heteropoly Acid H5PMo10V2040 Ronny Neumann* Casali Institute of Applied Chemistry, The Hebrew University of Jerusalem, Jerusalem, Israel 91904 Manfred Lissel* Facultat fur Chemie, Universitat Bielefeld, 4800 Bielefeld 1, Federal Republic of Germany Received February 28, 1989 The mixed addenda heteropoly acid H6PMoloV2040dissolved in 1,2-dichloroethane with tetraglpe, forming the (tetraglyme)~-H6PMolov20~complex, catalyzes the aromatization of cyclic dienes at moderate temperatures in the presence of molecular oxygen. Dehydrogenations of exocyclic dienes such as limonene show that dehy- drogenation is preceded by isomerization to their endocyclic isomers. Aromatization takes place by successive one-electron transfers and proton abstractions from the organic substrate to the heteropoly acid, the latter being reoxidized by dioxygen coupled with the formation of water. Introduction Table I. Oxidative Dehydrogenation of Hydrocarbonso Heteropoly acids and salts, especially those having a time, yield,* Keggin structure, have recently been increasingly reported substrate product h % as catalysts in both oxidative and acid-catalyzed trans- 9,lO-dihydroanthracene anthracene 16 >98, 89' formations.lp2 Heteropoly compounds as liquid-phase 9,lO-dihydroanthracene anthracene 24 - 1-2d oxidation catalysts have been used in various systems 9,lO-dihydrophenanthrene phenanthrene 5 >98 which may be classified by the type of oxidant and whether 9,lO-dihydrophenanthrene phenanthrene 24 - 1-2d the system has been photoactivated. One group of ap- 1,2-dihydronaphthalene (75%) naphthalene 5 >98 tetrahydronaphthalene naphthalene 24 0 plications involves the use of oxidizing reagents such as l,4-cyclohexadiene benzene 18 >98 hydrogen peroxide, tert-butyl hydroperoxide, or iodoso- 1,3-cyclohexadiene benzene 6 >98 benzene in the oxidation of alcohols, allyl alcohols, alkenes, cyclohexene benzene 24 0 and alkane^.^ The use of molecular oxygen coupled with 4-vinyl-1-cyclohexene ethylbenzene 24 22 photochemical activation represents a second set of reac- 1i m on en e p-cymene 20 >98, 7OC tions as in the dehydrogenation of alcohols, alkenes, or "Reaction conditions: 5 mmol of substrate, 1 mmol of tetra- alkane~.~The third area of research includes reactions glyme, 0.05 mmol of HSPMo10VZ040,10 mL of 1,2-dichloroethane, where the heteropoly compound acts as an electron ac- temperature = 70 "C, Pomsn = 1 atm. *Yields as computed by ceptor in what might be termed electron-transfer oxida- GLC. Isolated yields. dReaction performed at 1 atm of nitrogen. tions. In these transformations, oxidation of the substrate gas-phase dehydrogenation of aldehydes and carboxylic is achieved by successive one-electron transfers to the acids to form carbon-carbon double bonds a to the func- heteropoly anion. The reduced heteropoly compound is tional group5 or oxidation of sulfides to sulfoxides and substrate + HPC,, - product + HPCIed sulfones.6 In addition, substrates may be of an inorganic nature such as in the oxidation of bromide anions to mo- lecular bromine.' The substrate may also be a primary reoxidized by oxygen coupled with the formation of water catalyst such as Pd(0) (product is Pd(I1)) in a Wacker type to complete the catalytic cycle. Substrates in the context oxidation reaction! Generally, the most effective catalysts of the above reaction may be organic molecules as in the for this electron-transfer type of oxidation are the mixed addenda heteropolyanions of the formula H3+nPMo12-nVn040,PMoV-n, where n = 2-6. (1) (a) Pope, M. T. Heteropoly and Isopoly Oxymetallates;Springer In this paper we describe the use of H5PMoIoV20, Verlag: New York, 1983. (b) Day, V. W.; Klemperer, W. G. Science 1985, 228,533. (c) Pope, M. T. In Comprehensive Coordination Chemistry; dissolved in an apolar organic phase to catalyze the aro- Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon Press, matization of cyclic dienes by oxidative dehyrogenation New York, 1987; Vol. 3, Chapter 38. in the presence of dioxygen. In examples where the two (2) (a) Kozhevnikov, I. V.; Matveev, K. I. Russ. Chem. Reu. 1982,51, 1075. (b) Kozhevnikov, I. V.; Matveev, K. 1. Appl. Cat. 1983,5,135. (c) double bonds are not endocyclic, e.g. limonene, aromati- Kozhevnikov, I. V. Russ. Chem. Reo. 1987,56,811. (d) Misono, M. Cat. Reu. Sci. Eng. 1987, 29, 269. R (3) (a) Matoba, Y.; Ishii, Y.; Ogawa, M. Synth. Commun. 1984,14,865. I B (b) Yamawaki, K.; Yoshida, T.; Nishihara, H.; Ishii, Y.; Ogawa, M. Synth. Commun. 1986,16,537. (c) Hill, C. L.; Brown, R. B. J. Am. Chem. SOC. 1986,108,536. (d) Faraj, M.; Hill, C. L. J. Chem. SOC.,Chem. Commun. 1987,1487. (e) Furukawa, H.; Nakamura, T.; Inangaki, H.; Nishikawa, E.; Imai, C.; Misono, M. Chem. Lett. 1988, 877. (0 Schwegler, M.; Floor, I M.; van Bekkum, H. Tetrahedron Lett. 1988, 29, 823. (9) Ishii, Y.; R R Yamawaki, K.; Ura, t.; Yamada, H.; Yoshida, T.; Ogawa, M. J. Org. Chem. 1988,53,3587. (h) Faraj, M.; Lin, C.-H.; Hill, C. L. New J. Chem. 1988, (5) (a) Misono, M. In Proceedings of the Climax 4th International 12, 745. Conference on the Chemistry and Usage of Molybdenum; Barry, H. F., (4) (a) Papaconstantinou, E. J. Chem. SOC.,Chem. Commun.1982,12. Mitchell, P. C. H., Eds.; Climax Molybdenum Co.: Ann Arbor, 1982; p (b) Darwent, J. R. J. Chem. SOC.,Chem. Commun. 1982, 798. (c) Hill, 289. (b) Konishi, Y.; Sakata, K.; Misono, M.; Yoneda, Y. J. Catal. 1982, C. L.; Bouchard, D. A. J. Am. Chem. SOC.1985,107,5148. (d) Renneke, 77, 169. (c) Otake, M.; Onoda, T. Catalyst 1976, 18, 169. R. F.; Hill, C. L. J. Am. Chem. SOC.1986, 108, 3528. (e) Nomiya, K.; (6) Kozhevnikov, I. V.; Simagina, V. I.; Varnakova, G. V.; Matveev, K. Sugie, Y.; Miyazaki, T.; Miwa, M. Polyhedron 1986,5,1267. (f) Fox, M. I. Kinet. Catal. 1979,20, 416. A.; Cardona, R.; Gaillard, E. J. Am. Chem. SOC.1987, 109, 6347. (9) (7) Neumann, R.; &el, I. J. Chem. Soc., Chem. Commun. 1988,1285. Renneke, R. F.; Hill, C. L. New J. Chem. 1987,11,763. (h) Renneke, R. (8) (a) Matveev, K. I.; Kozhevnikov, I. V. Kinet. Catal. 1980,21,855. F.; Hill, C. L. J. Am. Chem. SOC.1988,110,5461. (i) Renneke, R. F.; Hill, (b) Matveev, K. I. Kinet. Catal. 1977,18,716. (c) Pachkovskaya, L. N.; C. L. Angew. Chem., Int. Ed. Engl. 1988,27, 1526. (j) Hiskia, A,; Pa- Matveev, K. I.; Il'inich, G. N.; Eremenko, N. K. Kinet. Catal. 1977, 18, paconstantinou, E. Polyhedron 1988, 7,477. 854. 0022-3263/89/1954-4607$01.50/0 0 1989 American Chemical Society 4608 J. Org. Chem., Vol. 54, No. 19, 1989 Neumann and Lissel 100 a 80 0 200 400 600 0 200 400 600 Time, min Time, min 6o 1 40120 0 100 200 300 200 400 600 Time, min Time, min 40 1 20 0 0 200 400 600 0 200 400 600 Time, mln Time, min Figure 1. Reaction profiles of the monoterpene dehydrogenation. Reaction conditions: 1mmol of monoterpene substrate, 0.25 mmol of tetraglyme, 0.01 mmol of H6PMoI0V2Om,2 mL of 1,2-dichloroethane, temperature = 70 "C, dioxygen or nitrogen pressure = 1 atm. Monoterpene substrate: (a) limonene (Oz),(b) limonene (Nz),(c) a-terpinene (02),(d) a-terpinene(Nz), (e) y-terpinene (OJ, (0 y-terpinene (N2). (A)Limonene; (0)a-terpinene; (0)y-terpinene; (0)terpinolene; (W) p-cymene. zation is preceeded by double-bond isomerization to an conditions with molecular oxygen in lieu of stoichiometric endocyclic position. reagents such as quinones (DDQ and p-~hloranil),~sele- nium, or sulfurlo or a high-temperature catalytic dehy- Results and Discussion drogenation with palladium or platinum." Further insight into the dehydrogenation reaction is The reaction system for the oxidative dehydrogenation gained by more carefully investigating the dehydrogenation reaction consists of the substrate, the H5PMo10V2040 of several monoterpene isomers such as limonene, 1, ter- catalyst dissolved in the presence of tetraglyme, CH30- pinolene, 2, a-terpinene, 3, and y-terpinene, 4, to p-cymene, (CH2CH20)4CH3,as complexing agent (see below), all in 5. The results of monoterpene dehydrogenation reaction 1,Zdichloroethane as solvent. Reactions are typically carried out at 70 "C under 1 atm of dioxygen. The results describing the aromatization of several substrates are given in Table I. Perusal of the results leads to the following observations. First, the cyclic dienes are dehydrogenated to the corresponding aromatic derivatives whereas the cyclic monoenes and saturated compounds are inert to dehydrogenation. Second, dioxygen is essential for the 1 2 3 4 5 catalytic cycle for there is no dehydrogenation (beyond the are given as reaction profiles in Figure 1. By examining stoichiometric amount of catalyst) in reactions carried out the profiles one may make the following observations. As under a nitrogen atmosphere. Third, the given catalyst described above in the absence of dioxygen there is no is unable to oxygenate any substrates under the given dehydrogenation although isomerization of the exocyclic conditions as no oxygenated products were found. This double bond occurs as can be seen in the isomerization of strongly indicates that dioxygen is not activated by the catalyst despite its being required for the reaction. Fourth, (9)Jackman, L. M.Adu. Org. Chem. 1960,2,329. conjugated dienes dehydrogenate more quickly than non- (10) (a) House, W. T.; Orchin, M. J. Am. Chem. Soc. 1960,82,639. (b) Silverwood, H. A.; Orchin, M. J. Org. Chem. 1962, 27, 3401. conjugated dienes. From a preparative synthetic point of (11)Rylander, P.N. Organic Syntheses with Noble Metal Catalysts; view this reaction enables a catalytic aromatization at mild Academic Press: New York, 1973.
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